JP2021104986A - Skin external composition - Google Patents

Abstract

To provide a technique for further improving a water-holding ability of epidermis.SOLUTION: A skin external composition contains a polymer and/or copolymer of a diallyl quaternary ammonium salt, and a water-holding agent. Preferably, the water-holding agent is an alkyl glycoside represented by the general formula (1) in the figure, where N represents an integer from 2 to 7, each R independently represents a hydrogen atom or C1-3 alkyl group, and n represents an integer from 1 to 4.SELECTED DRAWING: Figure 3

Description

The present invention relates to a composition for external use on the skin.

External skin compositions such as skin care cosmetics are expected to have an excellent feel on the skin after application. In particular, skin cleansers such as facial cleansers and cleansing agents are required to sufficiently remove stains such as make-up cosmetics and sebum, and also to have a good feel on the back skin. In particular, there is a demand for a moisturizing feeling without the skin becoming taut after washing.
Therefore, various moisturizers are added to the external composition for skin. As conventional moisturizers, components such as oils and polymers capable of forming a film for suppressing water evaporation on the skin surface, and components having water retention such as hyaluronic acid have been used.

By the way, in recent years, due to concerns about biological safety and environmental load, various sugar-based surfactants have been proposed as renewable and low environmental load, instead of conventional synthetic surfactants derived from petroleum raw materials. For example, the isoprenoid chain polyglycoside disclosed in Patent Document 1 has been proposed as a sugar-based surfactant whose craft temperature is lower than room temperature and whose balance between hydrophilicity and hydrophobicity can be widely controlled.
Further, Patent Document 2 describes that an oil-in-water emulsified composition containing an alkyl glycoside has an excellent moisturizing effect.

In addition, cationic polymers such as polymers obtained using dimethyldiallylammonium chloride as a monomer are widely used in external preparations for skin as a component that imparts smoothness to hair and the like.

Patent No. 3882067 Patent No. 6544956

In external composition for skin such as skin care cosmetics, it is desired to give a moisturizing feeling to the skin after application, but it cannot be said that the moisturizers conventionally used are sufficient.
In view of such a situation, we provide a technique for further improving the water holding capacity of the epidermis.

As a result of diligent research to solve the above problems, the present inventors have found that a specific cationic polymer has a property of storing a component that improves the water-holding ability of the epidermis in the epidermis, and as a result, We came up with the idea that the water holding capacity of the epidermis could be further enhanced, and completed the present invention.

That is, the present invention is as follows.
[1] A composition for external use on the skin, which contains a polymer and / or a copolymer of a diallyl quaternary ammonium salt and a water-holding agent.
[2] A composition for external use on the skin, wherein the water-holding agent is selected from alkyl glycosides, sucrose fatty acid esters, cellulose and its derivatives, and hyaluronic acid and its derivatives.
[3] The composition for external use on the skin according to [2], wherein the alkyl glycoside is an alkyl glycoside represented by the following general formula (1).

（式中、Ｎは２〜７の整数を表し、Ｒは独立して水素原子又は炭素数１〜３のアルキル基を表し、ｎは１〜４の整数を表す。）

(In the formula, N represents an integer of 2 to 7, R independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 4).

[4] The composition for external use on the skin according to any one of [1] to [3], wherein the diallyl quaternary ammonium salt is dimethyldiallyl ammonium chloride.
[5] The external application for skin according to any one of [1] to [4], wherein the polymer and / or copolymer of the diallyl quaternary ammonium salt is contained in an amount of 0.1 to 5% by mass based on the entire composition. Composition.
[6] The composition for external use on the skin according to any one of [1] to [5], which contains the water-holding agent in an amount of 0.01 to 1% by mass based on the entire composition.
[7] Any of [1] to [6], wherein the mass ratio of the content of the polymer and / or copolymer of the diallyl quaternary ammonium salt to the water-holding agent is 50: 1 to 1:10. The external composition for skin described in Crab.
[8] The composition for external use on the skin according to any one of [1 to [7], which is a cleansing agent.
[9] An agent for improving the skin retention of a water-holding agent, which contains a polymer and / or a copolymer of a diallyl quaternary ammonium salt.
[10] The skin retention improving agent according to [9], wherein the diallyl quaternary ammonium salt is dimethyldiallyl ammonium chloride.

The skin retention improver of the present invention stores the water-holding agent in the epidermis for a longer period of time or more. Therefore, the composition containing the skin retention improving agent of the present invention in combination with the water-holding agent is suitable for an external composition for skin having an excellent moisturizing effect because the water-holding ability of the epidermis can be further improved. In particular, since skin cleansing agents have a relatively shorter contact time with the skin than other skin care cosmetics, it is useful to be able to enhance the water-holding ability of the skin (epidermis) and give a moisturizing feeling in a short time. Become.

_{A graph showing the amount of Mal 2} Far in the supernatant when the amount of keratin powder was changed (100% was taken when the amount of keratin powder was 0 mg / mL). The graph which shows the dehydration amount per 1 g of keratin powder. The graph which shows the weight increase amount per 1 g of keratin powder.

The composition of the present invention contains a polymer and / or copolymer of a diallyl quaternary ammonium salt and a water-holding agent.

The polymer and / or copolymer of the diallyl quaternary ammonium salt refers to a polymer containing the diallyl quaternary ammonium salt as a monomer unit. As the diallyl quaternary ammonium salt, dimethyldiallyl ammonium chloride is more preferable.
Examples of the monomer unit other than the diallyl quaternary ammonium salt include acrylic acid, methacrylic acid, acrylamide, methacrylamide, and the like, but are not particularly limited.

Specific examples of the polymer or copolymer of the diallyl quaternary ammonium salt include, for example, a dimethyldialylammonium chloride polymer (polydimethylmethylene piperidinium) (polyquaternium-6), an acrylic acid amide / dimethyldialylammonium chloride copolymer weight. Coalescence (polyquaternium-7), dimethyldialyl ammonium chloride / acrylic acid copolymer (polyquaternium-22), acrylic acid / diallyl quaternary ammonium salt / acrylamide copolymer (polyquaternium-39), etc. are mentioned, and these are one kind. Alternatively, two or more types can be used.
The molecular weight of these polymers or copolymers is not particularly limited, and may be of a size usually used for external preparations for skin such as cosmetics. For example, a polymer having a molecular weight of 1000 to 10,000,000 measured under general conditions by GPC. Can be used.

The polymer or copolymer of the diallyl quaternary ammonium salt can retain the coexisting water-holding agent on the epidermis of the skin for a long time or in a large amount.
Therefore, the present specification provides a new application for improving the skin retention of a water-holding agent of a polymer and / or a copolymer of a diallyl quaternary ammonium salt. That is, another aspect of the present invention is an agent for improving the skin retention of a water-holding agent, which contains a polymer and / or a copolymer of a diallyl quaternary ammonium salt.

The content of the polymer and / or copolymer of the diallyl quaternary ammonium salt in the composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, based on the whole composition. 0.2 to 1.0% by mass is more preferable.
Further, the content of the polymer and / or copolymer of the diallyl quaternary ammonium salt in the composition of the present invention is 0 as the content of dimethyldiallyl ammonium chloride which is a monomer contained in the polymer. It is preferably 0.01 to 5% by mass, more preferably 0.05 to 3.0% by mass, still more preferably 0.1 to 1.0% by mass.
By using it in such a range, it becomes easy to store the water-holding agent longer or more in the epidermis (horny layer).

The water-holding agent in the present invention is not particularly limited as long as it can hold (store, bind, hydrate) water, and for example, alkyl glycosides, sucrose fatty acid esters, cellulose and its derivatives, and hyaluronic acid. And its derivatives and the like are preferably mentioned.

Alkyl glycosides are those in which an alkyl group is ether-bonded to a sugar residue.
Here, as sugar residues, galactose, xylose, mannose, lyxose, arabinose, fructose, maltose, xylobiose, isomaltose, cellobiose, lactose, gentiobees, maltotriose, isomaltotriose, cellotriose, maltotetraose, malt It is preferably selected from pentaose, maltohexaose, maltoheptaose, isomalttetraose, isomaltpentaose, isomalthexaose, and isomaltheptaose.
Further, examples of the alkyl group include an alkyl group having 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, and further preferably 10 to 16 carbon atoms, which may have a branch.

As the alkyl glycoside in the present invention, the alkyl glycoside represented by the following general formula (1) is more preferable.

In the general formula (1), N represents an integer of 2 to 7. R independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. n represents an integer of 1 to 4, preferably 2 or 3, and more preferably 2. That is, the alkyl glycoside represented by the general formula (1) has a structure in which the hydroxyl group at the 1-position of the sugar at the end of the oligosaccharide and the aliphatic alcohol are bonded (condensed).
The aliphatic alcohol is preferably an aliphatic alcohol having 12 to 20 carbon atoms, more preferably 12 to 16 carbon atoms, still more preferably 15 carbon atoms, and may have a branch.

The sugar residue in the alkyl glycoside represented by the general formula (1) is a hydrophilic portion.
Examples of sugar residues include maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose, with maltose and maltotriose being more preferred.

In the general formula (1), the fat chain is a hydrophobic portion in the alkyl glycoside according to the present invention.
The portion of the fat chain may or may not have a branched chain, but preferably has a branched chain. That is, in the general formula (1), R independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

As the alkyl glycoside according to the present invention, a compound represented by the following general formula (2) is more preferable.

In the general formula (2), N represents an integer of 2 to 7. n represents an integer of 1 to 4, more preferably n is 2 or 3, and even more preferably 2.
Examples of the compound included in the general formula (2) include Mal ₂ Far (glycoside form of maltose and hexahydrofarnesol), Mal ₃ Far (glycoside form of maltotriose and hexahydrofarnesol), and Mal ₃ Phyt (glycoside form of maltotriose and hexahydrofarnesol). (Glycoside compounds of triose and hexahydrophytol) and the like), but are not particularly limited.

As shown in the reference example described later, the alkyl glycoside according to the present invention can be bound (adsorbed) to keratin, which is the main component of the stratum corneum. Such binding is reversible and binds in a short time.
Further, in the stratum corneum to which the alkyl glycoside according to the present invention is bound, the water-holding ability is improved and the amount of water retained is increased, so that the barrier function of the skin is also expected to be improved.

The alkyl glycoside according to the present invention includes, for example, a glycosylation method using a bromide sugar, a glycosylation method using a fluoride sugar, a glycosylation method using trichloroacetoimidate, a glycosylation method using an acetylated sugar, and the like. It can be obtained by a well-known method, and more specifically, the synthesis steps described in Japanese Patent No. 3882067, Japanese Patent No. 4817435, Japanese Patent No. 5207420, Japanese Patent Application Laid-Open No. 2013-129660, Japanese Patent Application Laid-Open No. 2012-17318 and the like can be mentioned. Be done.

Examples of other water-holding agents for alkyl glycosides include sucrose fatty acid esters, cellulose and its derivatives, hyaluronic acid and its derivatives, and the like.
Examples of the sucrose fatty acid ester include mono-, di- or try esters of fatty acids having 8 to 18 carbon atoms and sucrose, and more specifically, polylauric acid sucrose, lauric acid sucrose, and myristic acid sucrose. , Sucrose palmitate, sucrose distearate, sucrose stearate and the like are preferable, but are not limited thereto.
Preferred examples of cellulose and its derivatives include, but are not limited to, cellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose and the like.
Hyaluronic acid and its derivatives preferably include, but are not limited to, hyaluronic acid, acetyl hyaluronic acid and the like.

The content of the water-holding agent in the composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.05 to 1% by mass, based on the whole composition.
By using it in such a range, it becomes easy to improve the water holding amount of the epidermis (horny layer).

The mass ratio of the content of the polymer and / or copolymer of the diallyl quaternary ammonium salt in the composition of the present invention to the water-holding agent is preferably 50: 1 to 1:10, more preferably 50: 1. ~ 1: 5, more preferably 30: 1 to 1: 1.
By containing them in combination in such a range, it becomes easier to improve the skin retention property of the water-holding agent.

The composition of the present invention has an effect that the skin retention property of the water-holding agent is improved by the action of the polymer and / or copolymer of the diallyl quaternary ammonium salt, and as a result, the water-holding ability of the skin (epidermis) is enhanced. Bring. Therefore, it is particularly preferable to use it externally on the skin.

The composition for external use on the skin is preferably in the form of a cosmetic or a quasi-drug, more preferably a skin care cosmetic, further preferably a cleansing agent, and more specifically, a cleansing agent, a face wash, a body soap, or a hand. Soap and the like can be mentioned.
The dosage form of the composition of the present invention is not particularly limited, and for example, liquid dosage forms such as lotions and essences, oil dosage forms, gel dosage forms, solid dosage forms, and emulsifier types such as emulsions and creams are preferable. Can be mentioned.

The composition of the present invention can be produced according to a conventional method.

The composition of the present invention may optionally contain other ingredients usually used in cosmetics as long as the effects of the present invention are not impaired. Such optional components include, for example, alcohols, ethers, powders, oils, moisturizers, surfactants, metal ion sequestering agents, pearling agents, amino acids, organic amines, polymer emulsions, pH regulators, vitamins, antioxidants. Examples include agents, preservatives, water-soluble polymers, fragrances, and various active ingredients.

Examples of alcohols include ethylene glycol, 1,3-butylene glycol, trimethylene glycol, 1,2-butylene glycol, propylene glycol, dipropylene glycol, propanediol, 1,2-pentanediol, 3-methyl-1, Divalent alcohols such as 3-butanediol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol; 3 such as trimethylpropane. Valuable alcohols; tetravalent alcohols such as pentaerythritol; pentavalent alcohols such as xylitol; polyhydric alcohol polymers such as triglycerin, tetraglycerin, and polyglycerin; sugar alcohols such as starch-degrading glycoreduced alcohols; polyglycerin;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl Alcohol alkyl ethers such as ether;
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol Alcohol alkyl ethers such as methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether;
Glycerin monoalkyl ethers such as xyl alcohol, ceracyl alcohol, and batyl alcohol;
Alcohol polymers such as diethylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, polyethylene glycol;
Glysolid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-butyl ether; POP / POE-butyl ether; Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphoric acid; POP / POE-pentane Examples include erythritol ether and the like.

As ether, in addition to those corresponding to the above alcohols
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether ,, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl Ether acetate, ethylene glycol diazibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl Examples thereof include ether acetate.

The shape of the powder is not particularly limited, such as spherical, needle-shaped, and plate-shaped. For example, inorganic powders (for example, talc, kaolin, mica, silk mica (serisite), white mica, gold mica, synthetic mica, etc. Red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, alumina, zeolite, barium sulfate, Calcined calcium sulfate (baked sekko), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, boron nitride, etc.; Organic powder (for example, polyamide resin powder (nylon powder), polyethylene powder, poly (meth) methyl acrylate powder, polystyrene) Powders, styrene and acrylic acid copolymer resin powders, silicone resin powders, benzoguanamine resin powders, polytetrafluoride ethylene powders, cellulose powders, etc.); Metal soaps (eg, zinc myristate, calcium palmitate, aluminum stearate) Inorganic white pigments (eg, titanium dioxide, zinc oxide, etc.); Inorganic red pigments (eg, iron oxide (Bengala), iron titanate, etc.); Inorganic brown pigments (eg, γ-iron oxide, etc.); Inorganic yellow Pigments (eg, yellow iron oxide, yellow clay, etc.); Inorganic black pigments (eg, black iron oxide, lower titanium oxide, etc.); Inorganic purple pigments (eg, mango violet, cobalt violet, etc.); Inorganic green pigments (For example, chromium oxide, chromium hydroxide, cobalt titanate, etc.); Inorganic blue pigments (for example, ultramarine blue, dark blue, etc.); Pearl pigments (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc) , Colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); Metal powder pigments (eg, aluminum powder, copper powder, etc.); Organic pigments such as zirconium, barium or aluminum lake (eg, Red 201, Red 202, etc.) , Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, and Blue 404. Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 No. and Blue No. 1 etc.); Natural pigments (For example, chlorophyll, β-carotene, etc.) and the like.

Examples of the oil agent include silicone oil, polar oil, natural oil, hydrocarbon oil and the like.

Examples of the silicone oil include dimethylpolysiloxane (dimethicone), cyclopentasiloxane, decamethylcyclopentasiloxane, caprylylmethicone, (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenylvinyldimethicone) crosspolymer and the like.

Polar oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, and lactic acid as synthetic ester oils. Cetyl, myristyl lactate, lanolin acetate, isosetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearyl, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl dicaprate Glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentanerythritol tetra-2-ethylhexylate, tri-2-ethylhexanoic acid Glyceryl, Trimethylol Propane triisostearate, Cetyl 2-Ethylhexanoate, 2-Ethylhexyl Palmitate, Glycerin Trimyristate, Glyceride Tri-2-Heptylundecanoic Acid, Himasi Oil Fatty Acid Methyl Estel, Oleic Acid Oil, Setostearyl Alcohol , Acetglyceride, 2-Heptylundecyl palmitate, Diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, Di-2-heptylundecyl adipate, Ethyllaurate, Di-2-sebatate Ethylhexyl, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebatate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, octylmethoxycinnamate And so on.

Natural oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, flaxseed oil, and sausage oil. Flower oil, cotton seed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, sunflower oil, triglycerin, glycerin trioctanoate, triisopalmitin Glycerin acid acid and the like can be mentioned.

Examples of the hydrocarbon oil include isododecane, isohexadecane, squalane, hydrogenated poly (C6-12) olefin, hydrogenated polyisobutene and the like.

Moisturizers include, for example, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, dl-pyrrolidone carboxylate, short chain soluble collagen, diglycerin (EO) PO. Additives, Izayoi rose extract, Hyaluronic acid extract, Merilot extract and the like can be mentioned.

Surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

Examples of the anionic surfactant include fatty acid sulphates (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, sodium lauryl sulfate, etc.). , POE lauryl sulfate triethanolamine, POE sodium lauryl sulfate, etc.); N-acylsarcosic acid (eg, sodium lauroyl sarcosin, etc.); higher fatty acid amide sulfonate (eg, N-myristoyl-N-methyltaurine sodium, palm oil, etc.) Fatty acid methyl taurid sodium, lauryl methyl taurid sodium, etc.); Phosphate ester salts (POE oleyl ether phosphate sodium, POE stearyl ether phosphoric acid, etc.); Sulfonic acid salts (eg, di-2-ethylhexyl sulfosuccinate sodium, mono Sodium lauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); Alkylbenzene sulfonate (eg, sodium linadodecylbenzene sulfonate, triethanolamine linadodecylbenzene sulfonate, linadodecylbenzene sulfonic acid, etc.) Higher fatty acid ester sulfate ester salts (eg, hardened coconut oil fatty acid sodium glycerin sulfate, etc.); N-acylglutamate (eg, N-lauroyl glutamate monosodium, N-stearoyl glutamate disodium, N-myristoyl-L-glutamate mono) Sodium, etc.); Sulfated oil (eg, funnel oil, etc.); POE alkyl ether carboxylic acid; POE alkyl allyl ether sulfonate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester salt; Higher fatty acid alkylolamide sulfate ester salt; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts. Polychloride (N, N'-dimethyl-
3,5-Methylene piperidinium); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkylmoriphonium salt; POE alkylamine; alkylamine salt; polyamine fatty acid derivative; amyl alcohol fatty acid Derivatives; benzalkonium chloride; benzethonium chloride and the like can be mentioned.

Examples of the amphoteric tenside include imidazoline-based amphoteric tenside agents (for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazolin sodium, 2-cocoyl-2-imidazolinium hydroki. Side-1-carboxyethyroxy disodium salt, etc.); Betaine-based surfactants (eg, 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine) , Sulfobetaine, etc.) and the like.

Nonionic surfactants include polyether-modified silicones (eg, polyethylene glycol-10 dimethicone, polyethylene glycol-12 dimethicone, etc.); polyglycerin-modified silicones (eg, polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 poly, etc.). Dimethylsiloxyethyl dimethicone, etc.); sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitane trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.; glycerin fatty acids (eg, monocotton oil fatty acid glycerin, monoerucate glycerin, sesquioleate glycerin, monostearate glycerin) , Α, α'-glycerin pyroglutamate oleate, glycerin maloic acid, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.); POE castor oil / cured castor oil derivative (POE castor oil, etc.) POE-hardened castor oil, etc.); Examples thereof include non-hydrophilic nonionic surfactants such as glycerin alkyl ether. Also, polyglycerin fatty acid esters (eg, polyglyceryl monooleate, polyglyceryl monostearate, etc.); POE sorbitan fatty acid esters (eg, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate, etc.); POE Solbit fatty acid esters (eg, POE sorbit monolaurate, POE sorbit monooleate, POE sorbit pentaoleate, POE sorbit monostearate, etc.); POE glycerin fatty acid esters (eg, POE glycerin monostearate, POE glycerin mono) POE monooleates such as isostearates and POE glycerin triisostearates; POE fatty acid esters (eg, POE distearates, POE monodiolates, ethylene glycol distearates, etc.); POE alkyl ethers (eg, POE lauryl ethers, POE oleyls, etc.) Ether, POE stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); POE alkylphenyl ethers (eg, POE nonylphenyl ether, etc.); POE / POP alkyl ethers (for example, POE / POP cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, etc.); Tetra POE -TetraPOP ethylenediamine condensates (for example, Tetronic)
POE castor oil cured castor oil derivatives (eg, POE castor oil, POE cured castor oil, POE cured castor oil monoisostearate, POE cured castor oil triisostearate, POE cured castor oil monopyroglutamic acid monoisostearic acid diester, POE hardened castor oil maleic acid, etc.); POE mitsuro / lanolin derivatives (eg, POE sorbit honeys, etc.); alkanolamides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acids Hydrophilic nonionic surfactants such as esters; POE alkylamines; POE fatty acid amides; sucrose fatty acid esters; other alkyl glycosides; alkylethoxydimethylamine oxides; trioleyl phosphates can also be mentioned.

Examples of the metal ion sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. , Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

Examples of the pearlizing agent include glycol distearate, titanium mica and the like.

Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of the amino acid derivative include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.

Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol and the like. Can be mentioned.

Examples of the polymer emulsion include an acrylic resin emulsion, an ethyl polyacrylate emulsion, an acrylic resin liquid, a polyacrylic alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of vitamins include vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin and the like.

Examples of antioxidants include tocopherols, dibutylhydroxytoluene (BHT), butylhydroxyanisole, pyrosulfate, gallic acid ester, phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, and fumaric acid. , Kefarin, hexametaphosphate, phytic acid, ethylenediamine tetraacetic acid and the like.

Examples of the preservative include parabens, phenoxyethanol and the like.

Examples of the water-soluble polymer include plant-based polymers (for example, Arabic gum, tragacant gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassaw extract), starch (rice). , Corn, potato, wheat), glycyrrhizinic acid); microbial macromolecules (eg, xanthan gum, dextran, succinoglucan, burran, etc.); animal macromolecules (eg, collagen, casein, albumin, gelatin, etc.), etc. Water-soluble polymer,
Cellulose-based polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); Cellulose-based polymers (hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose stearoxyether, sodium cellulose sulfate, carboxy) Methyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulosic powder, etc.); Semi-synthetic water-soluble polymers such as alginic acid-based polymers (eg, sodium alginate, propylene glycol alginate, etc.),
Vinyl-based polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymers, etc.); Polyoxyethylene-based polymers (for example, polyethylene glycol 20,000, 40,000, 60,000, etc.); Acrylic-based polymers Examples thereof include synthetic water-soluble polymers such as polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers.

Examples of various active ingredients include anti-inflammatory agents (eg, glycyrrhizinic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokithiol, zinc oxide, allantin, etc.); whitening agents (eg, placenta extract, yukinoshita extract, arbutin, etc.); Various extracts (eg, Oubaku, Ouren, Shikon, Shakuyaku, Senburi, Birch, Sage, Biwa, Carrot, Aloe, Zeniaoi, Iris, Grape, Yokuinin, Hechima, Yuri, Saffron, Senkyu, Shokyu, Otogirisou, Ononis, Garlic , Togarashi, tincture, tincture, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonylate valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin , Zingeron, cantalis tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclanderate, cinnaridine, trazoline, acetylcholine, verapamil, cepharanthin, γ-orizanol, etc. For example, sulfur, thiantol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

<Reference Example 1> Examination of binding property between keratin and alkyl glycoside It _{was examined whether alkyl glycoside (Mal 2} Far) binds to keratin, which is a main constituent of the stratum corneum, by the following procedure.
Take keratin powder (Keratin from wool K0044, manufactured by Tokyo Chemical Industry Co., Ltd.) in a 2 mL Eppendorf tube of 1.2, 6, 12, or 60 mg each, and _{add 1.2 mL each of 0.5 mg / mL Mal 2} Far aqueous solution to it. , 40 ° C. for 3 hours. The Eppendorf tube was centrifuged (15000 rpm, room temperature, 3 times for 3 minutes), and 1 mL of the supernatant was collected. _{The amount of Mal 2} Far not bound to keratin powder contained in the supernatant was quantified by Corona HPLC. The HPLC conditions are as follows.
Column: Atlantis T3 (100 x 3.0 mm, 3.5 μm)
Solvent: A: Water, B: Acetonitrile Gradient: B 10% (-30min) → 10% (0min) → 98% (30min) → 98% (35min)
Detection: Corona CAD
Flow velocity: 0.3 mL / min
Column temperature: 40 ° C
Syringe cleaning: 50% aqueous acetonitrile solution Inject: 1 μL

The results are shown in FIG. _{Since the amount of Mal 2} Far in the supernatant decreased depending on the amount of keratin powder, _{it was confirmed that Mal 2} Far and keratin powder were bound.

<Reference Example 2> Examination of water embrace of keratin to which alkyl glycoside is bound The water embrace of keratin to which alkyl glycoside (Mal ₂ Far) is bound was examined by the following procedure.
The weight of the petri dishes 1 to 3 was measured in advance. About 150 mg of keratin powder was weighed in Petri dish 1, _{and 3 mL of 0.5 mg / mL Mal 2} Far aqueous solution was further added. About 150 mg of keratin powder was weighed on a petri dish 2, and 3 mL of water was added. To the petri dish 3, 3 mL of a 0.5 mg / mL Mal ₂ Far aqueous solution was added. Petri dishes 1-3, 4
After incubating at 0 ° C. for 10 minutes, it was placed in a desiccator and dried under reduced pressure overnight. The weight (including the contents) of each petri dish after drying was measured, and the amount of dehydration per 1 g of keratin powder was calculated. The amount of dehydration per 1 g of keratin powder was calculated by the following formula.

The results are shown in FIG. Since _{the keratin powder to which Mal 2} Far was added was less likely to evaporate water than the keratin powder to which Mal ₂ Far was not added, it was confirmed that the water holding property of the stratum corneum to which Mal 2 Far was adsorbed was improved.

<Example 1> Examination of the effect of the composition of the present invention on water retention of keratin powder 2
The effect of the composition of the present invention on the water holding property of the stratum corneum was investigated by the following procedure.
The compositions shown in Table 1 were prepared by a conventional method.
Keratin powder was weighed in 0 mg or about 150 mg each on a petri dish that was weighed in advance. An aqueous solution obtained by diluting the composition of Example or Comparative Example contained in each petri dish 10-fold with water was added in an amount of 3 mL each, and the mixture was incubated at 40 ° C. for 10 minutes. Each petri dish after incubation was placed in a desiccator and dried under reduced pressure overnight. The weight (including the contents) of each petri dish after drying was measured, and the amount of weight increase per 1 g of keratin powder was calculated in the same manner as the amount of dehydration was calculated in Reference Example 2.

The results are shown in FIG. The keratin powder to which the composition of Example 1 was added was less likely to evaporate water than the keratin powder to which the compositions of Comparative Examples 1 to 3 were added, and a significant increase in the amount of water held was observed. From this, it was confirmed that the composition of the present invention further improves the water holding property of the stratum corneum.

The skin retention improver of the present invention stores the water-holding agent in the epidermis for a longer period of time or more. Therefore, the composition containing the skin retention improving agent of the present invention in combination with the water-holding agent is suitable for an external composition for skin having an excellent moisturizing effect because the water-holding ability of the epidermis can be further improved. In particular, since skin cleansing agents have a relatively shorter contact time with the skin than other skin care cosmetics, it is industrially possible to enhance the water-holding ability of the skin (epidermis) and impart a moisturizing feeling in a short time. Very useful.

Claims (10)

A composition for external use on the skin, which contains a polymer and / or a copolymer of a diallyl quaternary ammonium salt and a water-holding agent. A composition for external use on the skin, wherein the water-holding agent is selected from alkyl glycosides, sucrose fatty acid esters, cellulose and its derivatives, and hyaluronic acid and its derivatives. The composition for external use on the skin according to claim 2, wherein the alkyl glycoside is an alkyl glycoside represented by the following general formula (1).

(In the formula, N represents an integer of 2 to 7, R independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 4). The composition for external use on the skin according to any one of claims 1 to 3, wherein the diallyl quaternary ammonium salt is dimethyldiallyl ammonium chloride. The composition for external use on the skin according to any one of claims 1 to 4, which contains 0.1 to 5% by mass of the polymer and / or copolymer of the diallyl quaternary ammonium salt with respect to the entire composition. The composition for external use on the skin according to any one of claims 1 to 5, wherein the water-holding agent is contained in an amount of 0.01 to 1% by mass based on the entire composition. The invention according to any one of claims 1 to 6, wherein the mass ratio of the content of the polymer and / or copolymer of the diallyl quaternary ammonium salt to the water-holding agent is 50: 1 to 1:10. Skin external composition. The composition for external use on the skin according to any one of claims 1 to 7, which is a cleansing agent. A skin retention improving agent for a water-holding agent, which contains a polymer and / or a copolymer of a diallyl quaternary ammonium salt. The skin retention improving agent according to claim 9, wherein the diallyl quaternary ammonium salt is dimethyldiallyl ammonium chloride.

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